Experiment 32

Properties of carboxylic acids and esters

Background
Carboxylic acids are structurally like aldehydes and ketones in that they contain the
carbonyl group. However, an important difference is that carboxylic acids contain a
hydroxyl group attached to the carbonyl carbon.
O
C

OH

The carboxylic acid group

This combination gives the group its most important characteristic; it behaves as an acid.
As a family, carboxylic acids are weak acids that ionize only slightly in water. As
aqueous solutions, typical carboxylic acids ionize to the extent of only one percent or less.

O
R

O
OH + H2O

O + H3O+

At equilibrium, most of the acid is present as un-ionized molecules. Dissociation constants,

Ka, of carboxylic acids, where R is an alkyl group, are 105 or less. Water solubility
depends to a large extent on the size of the R-group. Only a few low-molecular-weight
acids (up to four carbons) are very soluble in water.
Although carboxylic acids are weak, they are capable of reacting with bases stronger
than water. Thus while benzoic acid shows limited water solubility, it reacts with sodium
hydroxide to form the soluble salt sodium benzoate. (Sodium benzoate is a preservative in
soft drinks.)
COO Na+ + H2O

COOH + NaOH
Benzoic acid

Sodium benzoate

Insoluble

Soluble

Sodium carbonate, Na2CO3, and sodium bicarbonate, NaHCO3, solutions can neutralize
carboxylic acids also.

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The combination of a carboxylic acid and an alcohol gives an ester; water is

eliminated. Ester formation is an equilibrium process, catalyzed by an acid catalyst.
O

CH3CH2CH2C OH + CH3CH2OH
Butyric acid

H2O + CH3CH2CH2C OCH2CH3

Ethyl alcohol

Ethyl butyrate (Ester)

Esterification
Hydrolysis

The reaction typically gives 60% to 70% of the maximum yield. The reaction is a reversible
process. An ester reacting with water, giving the carboxylic acid and alcohol, is called
hydrolysis; it is acid catalyzed. The base-promoted decomposition of esters yields an
alcohol and a salt of the carboxylic acid; this process is called saponification.
Saponification means soap making, and the sodium salt of a fatty acid (e.g., sodium
stearate) is a soap.
O
CH3CH2CH2C

O
OCH2CH3 + NaOH

CH3CH2CH2C

O Na+ + CH3CH2OH

Saponification

A distinctive difference between carboxylic acids and esters is in their characteristic

odors. Carboxylic acids are noted for their sour, disagreeable odors. On the other hand,
esters have sweet and pleasant odors often associated with fruits, and fruits smell the way
they do because they contain esters. These compounds are used in the food industry as
fragrances and flavoring agents. For example, the putrid odor of rancid butter is due to the
presence of butyric acid, while the odor of pineapple is due to the presence of the ester,
ethyl butyrate. Only those carboxylic acids of low molecular weight have odor at room
temperature. Higher-molecular-weight carboxylic acids form strong hydrogen bonds, are
solid, and have a low vapor pressure. Thus few molecules reach our noses. Esters,
however, do not form hydrogen bonds among themselves; they are liquid at room
temperature, even when the molecular weight is high. Thus they have high vapor
pressure and many molecules can reach our noses, providing odor.

Objectives
1. To study the physical and chemical properties of carboxylic acids: solubility,
acidity, aroma.
2. To prepare a variety of esters and note their odors.
3. To demonstrate saponification.

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Procedure
Carboxylic Acids and Their Salts
Characteristics of acetic acid
1. Place into a clean, dry test tube (100 13 mm) 2 mL of water and 10 drops of glacial
acetic acid. Note its odor by wafting (moving your hand quickly over the open end of the
test tube) the vapors toward your nose. Of what does it remind you?
2. Take a glass rod and dip it into the solution. Using wide-range indicator paper
(pH 112), test the pH of the solution by touching the paper with the wet glass rod.
Determine the value of the pH by comparing the color of the paper with the chart on
the dispenser.
3. Now, add 2 mL of 2 M NaOH to the solution. Cork the test tube and sharply tap it with
your finger. Remove the cork and determine the pH of the solution as before; if not
basic, continue to add more base (dropwise) until the solution is basic. Note the odor
and compare to the odor of the solution before the addition of base.
4. By dropwise addition of 3 M HCl, carefully reacidify the solution from step no. 3
(above); test the solution as before with pH paper until the solution tests acid. Does the
original odor return?
Characteristics of benzoic acid
1. Your instructor will weigh out 0.1 g of benzoic acid for sample size comparison. With
your microspatula, take some sample equivalent to the preweighed sample (an exact
quantity is not important here). Add the solid to a test tube (100 13 mm) along with
2 mL of water. Is there any odor? Mix the solution by sharply tapping the test tube with
your finger. How soluble is the benzoic acid?
2. Now add 1 mL of 2 M NaOH to the solution from step no. 1 (above), cork, and mix by
sharply tapping the test tube with your finger. What happens to the solid benzoic acid?
Is there any odor?
3. By dropwise addition of 3 M HCl, carefully reacidify the solution from step no. 2
(above); test as before with pH paper until acidic. As the solution becomes acidic, what
do you observe?
Esterification
1. Into five clean, dry test tubes (100 13 mm), add 10 drops of liquid carboxylic acid or
0.1 g of solid carboxylic acid and 10 drops of alcohol according to the scheme in Table
32.1. Note the odor of each reactant.

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Table 32.1

Acids and Alcohols

Test Tube No.

Carboxylic Acid

1
2
3
4
5

Formic
Acetic
Acetic
Acetic
Salicylic

Alcohol
Isobutyl
Benzyl
Isopentyl
Ethyl
Methyl

2. Add 5 drops of concentrated sulfuric acid to each test tube and mix the contents
thoroughly by sharply tapping the test tube with your finger.

CAUTION!
Sulfuric acid causes severe burns. Flush any spill with lots of water. Use gloves with this
reagent.

3. Place the test tubes in a warm water bath at 60C for 15 min. Remove the test tubes
from the water bath, cool, and add 2 mL of water to each. Note that there is a layer on
top of the water in each test tube. With a Pasteur pipet, take a few drops from this top
layer and place on a watch glass. Note the odor. Match the ester from each test tube
with one of the following odors: banana, peach, raspberry, nail polish remover,
wintergreen.
Saponification
This part of the experiment can be done while the esterification reactions are being
heated.
1. Place into a test tube (150 18 mm) 10 drops of methyl salicylate and 5 mL of
6 M NaOH. Heat the contents in a boiling water bath for 30 min. Record on the Report
Sheet what has happened to the ester layer (1).
2. Cool the test tube to room temperature by placing it in an ice water bath. Determine
the odor of the solution and record your observation on the Report Sheet (2).
3. Carefully add 6 M HCl to the solution, 1 mL at a time, until the solution is acidic. After
each addition, mix the contents and test the solution with litmus. When the solution is
acidic, what do you observe? What is the name of the compound formed? Answer these
questions on the Report Sheet (3).

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Chemicals and Equipment

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Glacial acetic acid

Benzoic acid
Formic acid
Salicylic acid
Benzyl alcohol
Ethanol (ethyl alcohol)
2-Methyl-1-propanol (isobutyl alcohol)
3-Methyl-1-butanol (isopentyl alcohol)
Methanol (methyl alcohol)
Methyl salicylate
3 M HCl
6 M HCl
2 M NaOH
6 M NaOH
Concentrated H2SO4
pH paper (broad range pH 112)
Litmus paper
Pasteur pipet
Hot plate

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